This application relates to an integrated process for the production of bisphenol A (BPA) from cumene hydroperoxide (CHP).
Bisphenol A is an important reactant used in the production of polycarbonate resins. A known method for the production of BPA involves the catalytic breakdown of CHP to phenol and acetone, and the subsequent reaction of the phenol and acetone in the presence of an acidic catalyst to form BPA. Various catalysts are known for use in each of these two steps.
Cleavage of CHP with homogeneous catalysts such as sulphuric acid is widely practiced. Heterogeneous cleavage of CHP over various solid acid catalysts has also been reported. For example, U.S. Pat. No. 5,824,622 discloses porous microcomposites of perfluorinated ion-exchange polymers and metal oxides, networks of silica, and networks of metal oxide and silica as catalysts and indicates that they can be used as catalysts, for example, for alkylating aliphatic or aromatic hydrocarbons, for decomposing organic hydroperoxides, such as CHP, for sulfonating or nitrating organic compounds, and for oxyalkylating hydroxylic compounds. PCT Publication WO 03/002499 refers to similar catalysts and demonstrates the not surprising result that reducing the particle size of the catalyst (and therefore increasing the catalytic surface area) enhances the reaction rates in decomposition of CHP and suggests the use of the same catalyst for both CHP decomposition and BPA synthesis. Other catalysts that can be used in the cleavage of CHP include solid acid catalysts such as zeolite beta, disclosed in U.S. Pat. No. 4,490,565; a Constraint index 1–12 zeolite, such as ZSM-5, disclosed in U.S. Pat. No. 4,490,566; faujasite, disclosed in EP-A-492807; smectite clays, described in U.S. Pat. No. 4,870,217; ion exchange resins having sulfonic acid functionality or heteropoly acids, such as 12-tungstophosphoric acid, on an inert support, such as silica, alumina, titania and zirconia, disclosed in U.S. Pat. No. 4,898,995. Additional solid-acid catalysts suited for use in the present invention include those comprising a sulfated transition metal oxide such as sulfated zirconia together with an oxide of iron or oxides of iron and manganese as described in U.S. Pat. No. 6,169,216, as well as those comprising a mixed oxide of cerium and a Group IVB metal, e.g., zirconium, described in U.S. Pat. No. 6,297,406. Other known solid acid catalysts comprise an oxide of a Group IVB metal modified with an oxyanion or oxide of a Group VIB metal by calcination of the oxide species at a temperature of at least 400.degree. C., as disclosed in U.S. Pat. No. 6,169,215. The modification of the Group IVB metal oxide with the oxyanion of the Group VIB metal imparts acid functionality to the material. The modification of a Group IVB metal oxide, particularly, zirconia, with a Group VIB metal oxyanion, particularly tungstate, is described in U.S. Pat. No. 5,113,034; and in an article by K. Arata and M. Hino in Proceedings of 9th International Congress on Catalysis, Volume 4, pages 1727–1735 (1988). The macroreticular acid ion exchange resin used is typified by the presence of sulfonic acid groups, e.g., the sulfonated styrene-divinylbenzene copolymer exchange resins such as those commercially available as Amberlyst-15, Amberlyst XN-1005, Amberlyst XN-1010, Amberlyst XN-1011, Amberlyst XN-1008 and Amberlite 200.
For catalyzing the formation of BPA from phenol and acetone, numerous sources disclose the use of cation exchange resin catalysts. For example, U.S. Pat. No. 5,315,042 discloses ion exchange resin catalysts such as sulfonated polystyrene or sulfonated poly(styrenedivinylbenzene) resins for this purpose. The use of divalent sulphur compounds such as mercaptans and glycolic acids to increase the reaction rate is also indicated. Sulphonated polystyrene-divinylbenzene ion-exchange resins with a portion of the sulphonic acid groups converted into mercaptan functionality were found better catalysts than unmodified resin (U.S. Pat. No. 3,172,916, U.S. Pat. No. 3,394,089). The use of zeolites coated with mercaptoamine at 120–180° C. has been reported (JP7420565). Singh (Catal. Lett., 27 (1992) 431) has discussed in detail the synthesis of BPA over zeolite catalysts such as H-ZSM-5, H-mordenite, H-Y and RE-Y vis-a-vis Amberlyst-15 and shown that zeolites with larger openings are more selective for this process although ion exchange resins are more active than zeolites. However, the general trend shows that modified ion exchange resins are the catalysts used worldwide for an optimum yield of bisphenol-A. Alkylation of propenyl halide with phenol using Friedel Crafts catalysts for the synthesis of BPA has been reported, (Fr. Demande 2,646,418, 1990). Conversions to the extent of 60% are obtained in the above mentioned process. Some monographs mention the use of commercial acid treated clays for the synthesis of bisphenol-A (Preparative Chemistry using Supported Reagents, Academic Press, San Diego, Calif., 1987, Solid Supports and Catalysts in Organic Synthesis, Ellis Horwood, Chechester, U.K., 1992). Scriabine et al. (U.S. Pat. No. 2,923,744) produce Bisphenol A using sulfuric acid, promoted by mercaptoalkanesulfonic acids or salts or corresponding sulfonate esters at a level of 0.1–5% by weight of the base charge, to catalyze condensation of acetone and phenols, when used in amounts of 0.1 to 5% by weight based on total charge. Sulfuric acid is used in amounts of about 2 moles per mole of acetone. The reactions can be run in halogenated hydrocarbon solvents. Bottenbruch et al. (U.S. Pat. No. 4,996,373) have proposed a process for producing dihydroxyaryl compounds from carbonyl compounds and phenols under high pressure, in the presence of various catalysts, including sulfonic acid resins. Catalysts containing thiol functionality, e.g. ion exchange resins treated with mercapto compounds, have been disclosed for this use. Meyer et al. (U.S. Pat. No. 4,387,251) have proposed processes for making 4,4′-dihydroxydiphenyl alkanes using aromatic sulfonic acids as condensing agents. Jansen (U.S. Pat. No. 2,468,982) has proposed preparation of bisphenols using anhydrous hydrogen chloride in combination with a mercaptoalkanoic acid, which may be formed in situ by reaction of a mercaptol with the ketone, as condensing agent. Knebel et al. (U.S. Pat. No. 4,931,594) disclose the use of large amounts of sulfonic acid resin, mixed with uncombined 3-mercaptopropionic acid, to cause the condensation to occur. It has been proposed in British Patent 1,185,223 to use a mixture of insoluble resins, one a sulfonic acid resin and the other a resin containing mercapto groups, for making bisphenols. Randolph et al. (U.S. Pat. No. 5,212,206) disclose a catalyst, made by treating a sulfonated ion-exchange resin with a dialkylaminomercaptan. Other references, representative of references on modification of sulfonic acid ion-exchange resins, include Wagner (U.S. Pat. No. 3,172,916). McNutt et al. (U.S. Pat. No. 3,394,089), Faler et al. (U.S. Pat. Nos. 4,455,409; 4,294,995 and 4,396,728); Heydenrich et al. (U.S. Pat. No. 4,369,293); Berg et al. (U.S. Pat. No. 5,302,774) and Maki et al. (U.S. Pat. No. 4,423,252). The reactive catalysts generally include mercapto-functions attached to a sulfonic acid group in the form of a sulfonamido or ammonium sulfonate salt.